Methods of making a lignocellulose product and products resulting therefrom



United States PatentfO? METHODS OF MAKING A LIGNOCELLULOSE PRODUCT AND PRODUCTS RESULTING THEREFROM William T. Glab, Dubuque, Iowa, assignor to Caradco Incorporated, a corporation of Iowa No Drawing. Filed Sept. 8, 1958, Ser. No. 759,388

8 Claims. (Cl. 106163) This invention relates to methods of making lignocellulose product and to the products resulting therefrom.

This application is a continuation-in-part of my copending application, Serial No. 443,711, filed July 15, 1954, now U.S. Patent No. 2,864,715.

. It is an object of this invention to provide an improved method of making a moldable composition comprising reacting an essentially dry mixture including comminuted lignocellulose and a reactant including dibasic ammonium phosphate to split at least a portion of the ligninfrom the lignocellulose while confining the mixture of lignocellulose and reactant under superatmospheric pressure.

Another object of this invention is to provide such a method wherein the reaction is conducted in an atmospher'eof steam at about 300-550 F. for about 4-60 minutes; a

:A. further object of the invention is to provide lignocellulose productsprepared by the above methods.

Other objects and advantages of the invention will be apparent from the following description of several embodiments of the invention.

An important advantage of the invention appears to be the controlling of'the reaction so that the alpha cellulose-is reduced in molecular size sufliciently to prevent swelling of subsequently fabricated products but not to the extent that toughness of fibre is lost. This latter occurs under drastic degradation and starts to become quite serious when approximately 25% of the lignocellulose has been lost as either gaseous or soluble by-products.

Another advantage appears to be the plasticization of the lignin component during the controlled cellulose degradation so that the lignin can subsequently vbe made to flow and function as a binder between the comrninuted lignocellulose particles.

'Another advantage is the provision of a relatively dry system so that high capacity for the processing of, for example, wood Waste is attained. This is not possible in a wet process such as ordinarily found in a pulping process in which the reactor is charged with approximately 90% water which takes up space as well as requires the addition of large amounts of energy to bring the reaction medium to the proper temperature. 7

Another advantage is the contacting of lignocellulose or dry mixes of lignocellulose and other ingredients under superatmospheric pressure with a vapor or combination of vapors functioning both as a heat transfer medium and as a reactant.

In the method of this invention an essentially dry mixture including comminuted lignocellulose and a reactant including dibasic ammonium phosphate is reacted as by heating while confining the lignocellulose and the reactant under superatmospheric pressure as in an autoclave.

During the reaction the lignocellulose'bond is apparently It appears that the hemi-celluloses-are the primary constituents of the lignocellulose which are. attacked by hydrolysis, but thatunder the high pressure, and temperature 'of this invention a portion of thehydrolysates are further converted to higher molecular weight materials not when it is molded. At the same time a controlled.

degradation of the alpha cellulose. is carried out to the extent that the desired degree of moisture stability is obtained in the molded or extruded products without an;

These actions are be-' batchwise in an autoclave or a sealed press or con tinuously in a continuous contactor.

The lignocellulose which appears dry to the touch actually contains up to about 30% water before the. reaction begins.

, The lignocellulose which may be used in this invention includes wood as well as other lignocellulosic vegetable materials. The lignocellulose is finely divided so that the particles are preferably not more than 20 mesh in size as measured by a standard screen although smaller sizes are preferred. 7

During the reaction which takes place in a confined atmosphere under superatmospheric pressure various reaction products are produced although the exact nature of the reactions is not understood. It appears that the reaction products are either inert so that the product itself is inert, have a binding action such as is true of the In the preferred process, steam is introduced into the autoclave both for heating purposes and to supply moisture for the reaction. In the high pressure method of this invention heat transfer is much more rapid so that in general a shorter reaction time is required. Furthermore, energy losses during the reaction are greatly re-' duced. In the ordinary reacting mixture these energy losses result from the release of volatile materials such as water vapor, gaseous reaction by-products and the like. As the reaction here takes place in a confined atmosphere, Further} no such losses occur to any material degree. more, the energy supplied by the steam or vapor is utilized to heat only the lignocellulose with its approximately normal moisture content in contrast to pulping type reactions where large quantities of Water are present, requiring far greater expenditures of energy.

Another important advantage of this process is the close control that is obtained over the reaction. Thus the;

temperature of the reacting mass, and hence the rate of reaction, can be easily raised or lowered by controlling the rate of fiow, pressure and the temperature of the heat transfer medium which may be steam, oil vapor, or other high temperature fluids. stopped by flashing the heat transfer medium from the autoclave since the large energy loss on expansion cools the reacting mass below the incipient reactionpoint. During the practice of the process the reaction mixture may be confined in a jacketed vessel with the heating medium introduced to the chambers in the quantity and temperature desired.

.Avery important advantage of the invention is that volatile. reactants may be used as the reacting mass is that volatile reactants may be used as the reacting mass is in 'a confined space. Volatile reactants are impossible,

of course, when the reacting mass is in the open.- As aresult, of the'rapid heattransfer. achieved by this inven tion and the penetration of volatile reactants the reaction which can function as plasticizers; for the autoclave prodnot only proceeds to completion in a much shorter time"- Patented Dec. 13, 1960 Reactions may easily be but the final product tends to be more uniform than where the reactants 'are heated such as in an ordinary'pro'cess that depends upon surface temperature differentials.

Tests have shown that the confining of the reacting mass in .the autoclave not only causes retention of the byproducts of reaction within the mass even when the byproducts are gaseous but also causes polymerization of all or a portion of these by-products, even some that are gaseous. In so-called wet processes large quantities of the by-products of reaction go into solution and are lost.

Another advantage of the invention is that the volatile by-products are easily collected and removed at low cost for later use where desired or to prevent the creation of a nuisance.

Where volatile reactants are used in conjunctionwith the ammonium phosphate no mechanical mixing of the ingredients is required. This results in a considerable saving in time, labor and other factors. Thus, in these instances,1it is only necessary to charge the reactor with the lignocellulose and introduce the volatile materials into the reactor under superatmospheric pressure. In addition, if desired, the reactants can be changed or modified during the course of a run. This is not possible to such a degree in a wet process where the charge generally contains less than 50% of lignocellulose, and addition of reactants would in many cases cause prohibitive amounts to go into solution.

TA further advantage of utilizing a vapor process is that the volatile content of the reaction product which is primarily moisture can be controlled. By using superheated steam with 'a sufficient degree of superheat, prod ucts ontheorder of 1% or lower volatile content can be obtained. Under normal'conditions, to degrees of superheat at 300 pounds per square inch steam pressure will produce a product of 3-5 volatile content. Thus the expensive drying step connected with wet processes canbe avoided.

Because of rapid penetration of reactants under high pressure, larger sized particles can be charged to'the autoclave "than would ordinarily be used, and a savings in size reduction cost made as a result of lower power requirements to reduce the treated material in comparison with raw lignocellulose.

'In addition, where fiat stock or preformed material is being made min a sealed press, the products can be made much thicker and more uniform than in an ordinary press'which depends'upon high platen temperatures for heat transfer, and in many cases requires almost prohibitive'cycle times.

The preferred reactants include dibasic ammonium phosphate, dibasic ammonium phosphate plus lignin, and dibasic phosphate plus Vinsol. Vinsol is defined in my copending application Serial No. 608,196, filed September 6, 1956, now Patent 2,872,330.

The products of the reactions ofthis invention may be finished shaped materials or moldable compositions that maybe used to make molded products. Where the prodnet is molded after the reaction, this product is preferably removed from the reaction vessel and then ground to a fine powder that is preferably not over 50 mesh in size. The finely divided moldablematerial is heated to a temperature just sufiicient to cause the material to flow and fill the mold under the pressure used. This temperature is kept sufficiently low, however, that losses are minor and breakdown due to decomposition is kept to a minimum. The preferred temperature is between 250-400" F.

The molding pressure may be any pressure sufficient to cause the material to fill completely the mold and *will vaiy dependingupon the shape'of the -mold, the nature of the moldablernaterial and other fac'tors. 'In, the prerel-red process to'prdduce high density materials this presisbetween 2000-101100 pounds pefsquare inch. ai i q s 't gi q lr fifisisn t nsei emoli able material "toifill the mold andset, "andagain will var dependingupon thetype 'ofmold being-used, the Itemperature, the nature or the moldable material and simi- Iar fac tors. In generahthe molding time wiuvar 'b'etween 0.2-15 minutes.

The How of the moldable material of this invention is improved and a shorter time is required if a plasticizer is added.

Plasticizers in general which have been found to lie effective with the moldable materials include water; aromatic compounds containing a hydroxyl group-such as aniline, phenol and cresol, alcohols such as benzyl, diethyleneglycol, glycerol, and furfuryl; nitrogen compounds such as formamide, urea, pyridine, and triethanolamine; and furfural.

The preferred plasticizers are water, furfural, aniline and phenol and the quantity utilized may vary depending on the flow desired. Thepreferred quantity is between about 2-20%. v

In particular, the choice of plasticizer will depend upon the end use or method of fabrication of the material. The reaction products themselves are of a slow thermosetting nature. Thus, if a plasticizer such as water which is incapable of thermoset is used, the material is essentially of a thermoplastic nature. This is also true of the preferred plasticizers as a group; however, when desired, thermoset compositions can be made by using furfural,

aniline or phenol in conjunction with a catalyst and, if.

desired, other materials capable of copolymerization.

Materials which will function as catalysts include'the oxides, hydroxides and carbonates of the alkali and alkaline earthnmetals. The preferred catalysts are the oxides of magnesium and zinc.

Among. the materials which may be used with the thermosetting plasticizers as copolymers'are 'hexamethylene tetramine, dimethylolurea, paraformaldehyde and" urea.

Depending upon the set time required, about 05-50% of the catalyst and about 05-10% of the copolymer'are used.

If desired, thermoset products can be obtained without the use of catalysts or copolymers merely by heat treating the fabricated products after they have been molded or extruded.

If desired, products of density ranging from 0.2-1.3 specific gravity may be produced in the high pressure reacting vessel itself without requiring a subsequent molding operation as described above with high pressure. molding. Here the finely divided lignocellulose and the re:

actant are mixed where the reactant is a solid or liquid and the mixture cold pressed into the desired shape or compacted in a sealed press. The compressed mixture is then heated in the press or other high pressure vessel for the required time at the required temperature and pressure. The material when removed from the reaction vessel will then be found to be quite hard and strong. In these instances, the reactant may be any of those set out above.

The preferred amount of ammonium phosphate varies between about 110% by weight of the lignocellulose. When lignin is also used, the amount of lignin is between about 2-20% by weight of the lignocellulose. Where Vinsol is used in conjunction with dibasic ammonium phosphate the preferred amount of Vinsol is between about 2-20% by weight of the lignocellulose.

Steam may or may not be supplied to the reaction vessel depending upon the result desired. If steam is used, it is preferably supplied at 100-1000 pounds per square inch pressure and at a temperature of 400-550 F. In the event that a sealed press is used, the normal moisture content of the wood as well as the reaction by-products'may be used to build up to a predetermined pressure which can be maintained constant by venting the excess vapors produced. This pressure is "preferably between 100-600 pounds per square inch. vSuch a procedure eliminates the 6% of finely divided by-product lignin. The mixture was placed in a steel cylinder that had -a continuous baflled port on the inner wall to which was connected a pressure line fitted with a pressure gauge and a valve. Gaskets were placed on both ends of the cylinder, and steel stops were placed on the top and bottom of the material so that it would be compressed below the depth of the cylinder when the device was placed in a hot press.

A number of experiments were conducted according to the method of this example. In one experiment the press was heated to 450 F., the press closed on the gaskets and the material was allowed to develop its own pressure as a result of the reaction. No external steam was introduced into the ring. The pressure was permitted to rise to 400 pounds per square inch where it was held substantially constant by venting the excess pressure. The cylinder took approximately minutes to reach this pressure, and the material was held confined in the press for a total of 25 minutes. When the product was removed, it was found to be very dark, tough and uniform. It had a density of 50 pounds per cubic foot and a modulus of rupture of Density of .Prod- Modulus of Rup- Pressure uct,1b. per ture,1b. per cu. ft. sq. in.

;'Thus, the beneficial elfect of increased pressure is readi ly apparent, and the runs prove that an ordinary hot press fitted with gaskets can be used as an autoclave for'the;

The introduction;

single stage production of materials. of steam at the start of the press cycle rather than depending on the material for development of pressure drastically reduces cycle time. In addition, control of the press proces's'is greatly increased by control of vapor pressure which is impossible in an open press.

In the methods of this invention the high pressure reaction may be used to treat the lignocellulose prior to molding but may also be used to chemically treat the' lignocellulose without molding as the treated'material itself has other uses such as employment as fillers in various plastic compositions. The method may also be used to produce products of a wide range of densities wherein the high pressure reaction and shaping is carried on at the same time. 1

Where the reaction takes place in an atmosphere of steam the volatile content of the resulting product may be reduced by using superheated steam. There is, of course, very littlecondensation with superheated steam. Thefollowing table'shows the reduction obtained in the volatile content of the product by operating with super-. heatedsteamrw Autoclave Time- Pressure, Percent Run No. Mins. Temp., F. p.s.i. Volatile Content All of the above runs were made with plain lignocellulose, but are typical of the results in general.

It was also found that when the reaction pressure is increased, the reaction time was considerably decreased. Thus, where ground lignocellulose was used with steam at 300 pounds per square inch and about v42545() F. temperature as a reactant the reaction time was found to be 20 minutes at this 300 pounds per square inch pressure. When the pressure was increased to 400 pounds per square inch, the reaction time was only about- 7 minutes. Where the steam pressure was increased to 500 pounds per square inch, the reaction time was reduced to between 4-5 minutes. These steam pressures were all gauge pressures.

EXAMPLE 2 To 500 grams of 20 mesh, hammermilled ponderosa pine, containing only its normal moisture content of approximately 6% was added grams of a 10% solution of dibasic ammonium phosphate in water. Based on the .weight of the lignocellulose the amount of solution, was

approximately 20% and the dibasic ammonium phosphate was approximately 2%. The mixture was ballrnilled forfapproximately' /2'h'our to obtain a uniform dispersion ofthe dibasic ammonium phosphate throughout the mass. 'Ihis composition :was then placed in a heated autoclave, and steamwas admitted until the pres-'' sure was 300 pounds per square inch gauge, and the'.

temperature was approximately 425 F. The autoclave was held under these conditions for 15 minutes, and

then the steam was rapidly flashed ofi. During the course of the run, the pressure was maintained at 300 psi. by venting off the excess pressure caused by volatile reaction by-products. The granular reaction product,

which had been cooled below the incipient reaction pointby the rapid steam flash-off, was removed from the autoclave, and all particles which had consolidated were 4 thoroughly broken up. The moisture or volatile con tent of this material was approximately 10%.

In the same manner as specified for Example 2, re action products of lignocellulose and Vinsol, and lignocellulose" and lignin in the presence of dibasicammonium phosphate were prepared. With both Vinsol and lignin dibasic ammonium phosphate solution.

was added.

To determine the effect of dibasic ammonium ph0sphate, as well as Vinsol and lignin, controls were run in which only 20 mesh ponderosa pine was autoclaved" in the same manner as Example 2. The following table sets forth the autoclave conditions and reaction times for containing Vinsol the controls, as well as for the runs and lignin.

Percent Autoclave Dibasie Reac- Run Ammo- I tion Example No. No. nium Additive Time, Tem- Pres- Phos- Min. para sure, phate tu're, p.s1i.

Control A (472) None None 20 440 300-" Control B...- (146) do .do 30 .4451 300 (4 5% ,VinsoL 20 .440 300 5%Lig1in. 20 440' 300 agcecme r The reaction products from Examples 2, 3 and 4 as well as controls A and B were then evaluated by pressing them into boards, and testing the boards to determine their moisture resistance and strength. The boards were 8 I claim: 1. The method of making a lignocellulose product, consisting essentially of: intimately mixing particles of essentially dry lignocellulose with between about 1-10% of formed by placing 80 grams of the reaction products into ammonium phosphate by weight of the lignocellulose; a. 4 x 5 x A-inch high-steel frame, and leveling the maand heating the resulting composition under a pressure terial. A 4 x 5-inch steel plug heated to the press ternof between about 100-1000 pounds per square inch in a perature was then placed on top of the material, and confined atmosphere in the presence of steam at a temthis assembly was put into a hot press. The following perature of about 300-550 F. for about 4-60 minutes table sets forth the press temperature, pressure and time to combine chemically said phosphate with the lignocelcycle that was used for the various reaction products, lulose. 7 along with the results of the physical property tests which 2. The method of making a lignocellulose product, conwere made with the boards. The dimensional stability sisting essentially of: intimately mixing particles of essenin the presence of moisture was determined in both a tially dry lignocellulose with between about 1-10% of l-hour {boil and a 48-hour immersion test. In addition, dibasic ammonium phosphate by weight of the lignocelluthe boards were tested in flexure to obtain their modulus lose; and heating the resulting composition under a presof rupture. sure of between about 100-1000 pounds per square inch Increase from Increase from 48- Boil Test hour Immersion Board Percent Time, Temp., Press, Density, M.R. Material Example No. Phos- Min. F. p.s.l. lbs/ft. p.s.i.

phate Wt., Thick., Wt;., Thick, DEF percent DH- percent cent cent ControlA (543) None 10 400 40 42.5 393 74.8 16.5 75.5 5.2 Control 13.... E55 10 400 40 39.0 247 92.3 19.7 84.8 4.9 2 005) 2 10 400 40 40.2 420 72.3 8.7 30.2 3.1 3.. (608) 2 10 400 40 50.0 745 41.8 6.1 46.8 3.1 4 (607) 2 10 400 40 46.6 593 57.0 9.5 58.9 4.1

From the foregoing table it is apparent that the dimenin a confined atmosphere in the presence of steam at a siona-l stability exhibits a decided improvement when temperature of about 300-550 F. for about 4-60 minutes dibasic ammonium phosphate is reacted with the lignoto combine chemically said phosphate with the lignocellucellulose. Where Vinsol or lignin are included the comlose. pressibility is improved so that a stronger bond results. 3. The method of making a lignocellulose product, The reaction temperatures and times are controlled consisting essentially of: intimately mixing particles of as desired to produce flow of moldability in the autoessentially dry lignocellulose with about l-10% ammoclave product and strength and stability in the final nium phosphate and about 2-20% lignin, both being by product. Thus, where the product is to be used as a Weight of the lignocellulose; and heating thevresulting molding material, it was discovered that under the above composition under-a pressure of between about 100-1000 conditions with plain lignocellulose a reaction time of pounds per square inch in the presence of steam for beless than 20 minutes resulted in poor fiow, But at this tween about 4-60 minutes and at between about 300-550 same stream pressure and using the same lignocellulose 4 F. to combine chemically said phosphate and the lignin a reaction time of over 30 minutes produced a high with the lignocellulose. quality moldable product. Apparently steam breaks 4. A lignocellulose product prepared by the method of down the lignocellulose so that the lignin acts as a binder im while some of the hydrolized products of the reaction A lignocellulose product p p y the et o operate as plasticizers. In the high pressure confined atof claim 3- mosphere method of this invention, these reaction prod- 6. The method of making a lignocellulose product, nets are primarily retained. In the prior processes where consisting essentially of: intimately mixing particles of a hydrolizing reaction was carried out either in the atessentially dry lignocellulose with between about 1-10% mosphere or in a slurry, many of the by-products either of ammonium phosphate and between about 2-20% of a passed off as gases or were dissolved and removed i finely divided solvent extracted solid pine wood resin subthe liquid. Thus by avoiding excess water the process stalltially free of Wood rosin, Said amounts being y Weight of this invention results in the saving of substantial porof the lignocellulose; and heating the resulting compositions of the hemi-celluioses and makes them available tion llfldfir Pressure of between about loo-1000 Pound8 for use as plasticizers. However, if the reaction is P Square inch in a confined atmosphere in the P1135311ce carried on too long a time at too high a te eratu e, of steam at atemperature of about 300-550 F. for about the hemi-celluloses and other hydrolized products of minutes to COHlbiTle chemically Said Phosphate with the reaction tend to polymerize so that the final product the lignocelluloseexhibits lack of fiow and is difiicult to mold. The nature The method of making 59109811111036 P 6011- of these polymerizates is not completely under t od sisting essentially of: intimately mixing particles of essen- Thus one of the advantages of th process f hi 65 tially dry lignocellulose with about 1-10% of dibasic aminvention is that it reduces losses of the lignocellulose monillm P p and between about 2-20% of afinely and, furthermore, permits the use of lower moldin r divided solvent extracted solid pine wood resin substansures and temperatures when the reaction product is used i l y free of Wood rosin, Said amounts being y Weight as a molding composition. of the lignocellulose; and heating the resulting composi- H i described my invention as related to h tion under a pressure of between about 100-1000 pounds bodiments set: out herein, it is my intention that the P r square inch in a confined atmosphere in the presence invention-be not'limited by any of the details of descripof steam at a temperature ofabout 300-550 F. for about tion unless otherwise specified, out rather be construed minufes to combine chemically Said PhOSPhtlte with broadly within its spirit and scope as set out in the acthe lignocellulosecompanying 91m. 8. The method of making a lignocellulose product, consisting essentially of: intimately mixing particles of essentially dry lignocellulose with about 1l0% of ammonium phosphate, about 220% lignin, and between about 220% of a finely divided solvent extracted solid pine wood resin substantially free of wood rosin, said amounts 5 being by weight of the lignocellulose; and heating the resulting composition under a pressure of between about 100-1000 pounds per square inch in a confined atmosphere in the presence of steam at a temperature of about BOO-550 F. for about 4-60 minutes to combine chemi- 10 cally said phosphate with the lignocellulose.

References Cited in the file of this patent UNITED STATES PATENTS Othmer et a1 Oct. 19, 1954 Gill Jan. 29, 1957 Glab Feb. 3, 1959 FOREIGN PATENTS Canada July 31, 1956 Great Britain Dec. 16, 1938 

1. THE METHOD OF MAKING A LIGNOCELLULOSE PRODUCT, CONSISTING ESSENTIALLY OF: INTIMATELY MIXING PARTICLES OF ESSENTIALLY DRY LIGNOCELLULOSE WITH BETWEEN ABOUT 1-10% OF AMMONIUM PHOSPHATE BY WEIGHT OF THE LIGNOCELLULOSE, AND HEATING THE RESULTING COMPOSITION UNDER A PRESSURE OF BETWEEN ABOUT 100-100 POUNDS PER SQUARE INCH IN A CONFINED ATMOSPHERE IN THE PRESENCE OF STEAM AT A TEMPERATURE OF ABOUT 300-550*F. FOR ABOUT 4-60 MINUTES TO COMBINE CHEMICALLY SAID PHOSPHATE WITH THE LIGNOCELLULOSE. 